US8168699B2 - Solvent-assisted continuous emulsification processes for producing polyester latexes - Google Patents
Solvent-assisted continuous emulsification processes for producing polyester latexes Download PDFInfo
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- US8168699B2 US8168699B2 US12/819,462 US81946210A US8168699B2 US 8168699 B2 US8168699 B2 US 8168699B2 US 81946210 A US81946210 A US 81946210A US 8168699 B2 US8168699 B2 US 8168699B2
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- United States
- Prior art keywords
- resin
- ether
- extruder
- polyoxyethylene
- mixture
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 71
- 230000008569 process Effects 0.000 title claims abstract description 63
- 229920000728 polyester Polymers 0.000 title abstract description 27
- 239000002904 solvent Substances 0.000 title abstract description 18
- 238000004945 emulsification Methods 0.000 title description 9
- 229920005989 resin Polymers 0.000 claims description 165
- 239000011347 resin Substances 0.000 claims description 165
- 239000000203 mixture Substances 0.000 claims description 151
- -1 tetrahydrohyran Chemical compound 0.000 claims description 123
- 239000002245 particle Substances 0.000 claims description 64
- 239000004816 latex Substances 0.000 claims description 62
- 229920000126 latex Polymers 0.000 claims description 62
- 239000003795 chemical substances by application Substances 0.000 claims description 55
- 239000000839 emulsion Substances 0.000 claims description 53
- 239000004094 surface-active agent Substances 0.000 claims description 49
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 39
- 230000003472 neutralizing effect Effects 0.000 claims description 39
- 229920001225 polyester resin Polymers 0.000 claims description 39
- 239000004645 polyester resin Substances 0.000 claims description 38
- 239000004014 plasticizer Substances 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 25
- 229920006127 amorphous resin Polymers 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 24
- 229920006038 crystalline resin Polymers 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 150000002148 esters Chemical class 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 150000001408 amides Chemical class 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001298 alcohols Chemical group 0.000 claims description 10
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007764 o/w emulsion Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- HYTRYEXINDDXJK-UHFFFAOYSA-N Ethyl isopropyl ketone Chemical compound CCC(=O)C(C)C HYTRYEXINDDXJK-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical class [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 8
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 8
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 150000002170 ethers Chemical class 0.000 claims description 7
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 6
- 229960000686 benzalkonium chloride Drugs 0.000 claims description 6
- 150000001555 benzenes Chemical class 0.000 claims description 6
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- 150000008039 phosphoramides Chemical class 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 235000011181 potassium carbonates Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 150000003457 sulfones Chemical class 0.000 claims description 6
- 150000003462 sulfoxides Chemical class 0.000 claims description 6
- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical class [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 125000006177 alkyl benzyl group Chemical group 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- WMLFGKCFDKMAKB-UHFFFAOYSA-M benzyl-diethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](CC)(CC)CC1=CC=CC=C1 WMLFGKCFDKMAKB-UHFFFAOYSA-M 0.000 claims description 5
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 5
- 239000011736 potassium bicarbonate Substances 0.000 claims description 5
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 5
- 150000003871 sulfonates Chemical class 0.000 claims description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 5
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 4
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 4
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 229940105329 carboxymethylcellulose Drugs 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 235000010980 cellulose Nutrition 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- SMQZZQFYHUDLSJ-UHFFFAOYSA-L disodium;1-dodecylnaphthalene;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.C1=CC=C2C(CCCCCCCCCCCC)=CC=CC2=C1 SMQZZQFYHUDLSJ-UHFFFAOYSA-L 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 4
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
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- 229940016409 methylsulfonylmethane Drugs 0.000 claims description 4
- 229920002114 octoxynol-9 Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims 1
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- 238000001125 extrusion Methods 0.000 abstract description 2
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- 230000002776 aggregation Effects 0.000 description 22
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 21
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- 235000014113 dietary fatty acids Nutrition 0.000 description 11
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- 229960001939 zinc chloride Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0802—Preparation methods
- G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
- G03G9/0806—Preparation methods whereby the components are brought together in a liquid dispersing medium whereby chemical synthesis of at least one of the toner components takes place
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08755—Polyesters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
Definitions
- the present disclosure relates to processes for producing resin emulsions useful in producing toners. More specifically, solvent-assisted continuous processes are provided for emulsification of high yield polyester resins utilizing extruders.
- Emulsion aggregation is one such method.
- Emulsion aggregation toners may be used in forming electrophotographic images.
- Emulsion aggregation techniques may involve the formation of a polymer emulsion by heating a monomer and undertaking batch or semi-continuous emulsion polymerization, as disclosed in, for example, U.S. Pat. No. 5,853,943, the disclosure of which is hereby incorporated by reference in its entirety.
- Other examples of emulsion/aggregation/coalescing processes for the preparation of toners are illustrated in U.S. Pat. Nos.
- Polyester toners have been prepared utilizing amorphous and crystalline polyester resins as illustrated, for example, in U.S. Patent Application Publication No. 2008/0153027, the disclosure of which is hereby incorporated by reference in its entirety.
- the incorporation of these polyesters into the toner requires that they first be formulated into emulsions prepared by solvent containing batch processes, for example solvent flash emulsification and/or solvent-based phase inversion emulsification (PIE), which are both time and energy-consuming.
- solvent flash emulsification and/or solvent-based phase inversion emulsification (PIE) solvent-based phase inversion emulsification
- PIE solvent-based phase inversion emulsification
- large amounts of organic solvents such as ketones or alcohols, have been used to dissolve the resins, which may require subsequent energy intensive distillation to form the latexes, and are not environmentally friendly.
- process inputs i.e. resin acid value
- noise variables i.e. solvent evaporation, NH 3 evaporation
- variation in the lot-to-lot resin acid value may require different process input variations (i.e. neutralization ratio, solvent ratio) to achieve the desired particle size and may require extensive work before a resin lot is scaled-up.
- process input variations i.e. neutralization ratio, solvent ratio
- the individual batch process involves the handling of bulk amounts of materials, and each process may take many hours to complete before moving to the next process in the formation of the toner, that is, aggregation and/or coalescence.
- batch-to-batch consistency is frequently difficult to achieve because of variations that may arise from one batch to another.
- Solventless latex emulsions have been formed in either a batch or extrusion process through the addition of a neutralizing solution, a surfactant solution and water to a thermally softened resin as illustrated, for example, in U.S. Patent Application Publications Serial Nos. 2009/0246680 and 2009/0208864 the disclosures of each of which are hereby incorporated by reference in their entirety.
- a small amount of coarse material often remains un-emulsified in these processes and so the conversion of the resin to the latex may not be complete.
- the latexes therefore may be treated to remove this coarse content, or a polishing step may be added to convert the residual resin or coarse material into latex particles.
- filtration may be used to remove any coarse material
- ultrasonication and/or homogenization using external high shear devices may be applied to the latex produced from the extruder to complete the conversion.
- additional process steps are, however, not desirable as they add complexity, energy consumption and cost.
- conventional processes have limited applicability with respect to the choice of polyester resin.
- certain resins degrade during the process based on their molecular weight and composition, leading to latexes with polymers of lower molecular weight than the starting material. While not wishing to be bound by theory, the polyester degradation is thought to be the result of base-induced hydrolysis of the polyester backbone.
- Solvent-assisted continuous processes for forming high yield, low coarse content, polyester latexes are disclosed which may be utilized in forming a toner.
- a process of the present disclosure may include contacting at least one polyester resin with a plasticizer to form a pre-blend mixture, neutralizing the pre-blend mixture with a neutralizing agent, contacting the pre-blend mixture with a surfactant, melt-mixing the pre-blend mixture, contacting the melt-mixed mixture with de-ionized water to form an oil in water emulsion possessing latex particles, and continuously recovering the latex particles.
- a process of the present disclosure may include contacting at least one polyester resin with a plasticizer in a first section of an extruder comprising an organic solvent selected from the group consisting of alcohols, ketones, amides, nitriles, ethers, sulfones, sulfoxides, phosphoramides, esters, benzenes, and amines, present in an amount of from about 5% by weight to about 100% by weight of the at least one polyester resin to form a resin mixture, neutralizing the resin mixture in a second section of the extruder with a solid neutralizing agent selected from the group consisting of ammonium hydroxide, potassium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, lithium hydroxide, potassium carbonate, potassium bicarbonate, organoamines, and combinations thereof, contacting the resin mixture with a surfactant in the extruder, melt-mixing the resin mixture in the extruder, contacting the melt-mixed mixture with de-ionized water to
- a process of the present disclosure may include contacting at least one polyester resin with a plasticizer in an extruder, the plasticizer comprising an organic solvent selected from the group consisting of alcohols, ketones, amides, nitriles, ethers, sulfones, sulfoxides, phosphoramides, esters, benzenes, and amines, present in an amount of from about 5% by weight to about 100% by weight of the polyester resin to form a resin mixture to form a resin mixture, neutralizing the resin mixture in the extruder with a neutralizing agent, contacting the resin mixture in the extruder with a surfactant in the extruder, melt-mixing the resin mixture in the extruder, contacting the melt-mixed mixture with de-ionized water in the extruder to form an oil in water emulsion possessing latex particles, and continuously recovering the latex particles from the extruder.
- the plasticizer comprising an organic solvent selected from the group consisting of alcohols, ketones, amide
- the FIGURE is a schematic diagram of an extruder for preparation of a polyester latex according to embodiments of the present disclosure.
- the present disclosure provides processes for forming an emulsion with a high solids content.
- the resulting emulsion may then be used for forming a toner, paint, powder, coating, compounding additive for pharmaceuticals, encapsulant for a drug, adhesive, or food additive via a continuous process.
- the present disclosure provides a continuous process which includes co-feeding at least one polyester resin with at least one plasticizer, such as a solvent or a wax, and a neutralizing agent into a screw feeder or an extruder to form a pre-blend mixture; contacting the pre-blend mixture with water and a surfactant; melt-mixing the mixture; contacting the melt-mixed mixture with additional water at a plurality of subsequent intervals to form an emulsion; and continuously recovering latex particles having low coarse content.
- plasticizer such as a solvent or a wax
- the present disclosure provides a continuous process which includes co-feeding at least one polyester resin with at least one plasticizer, such as a solvent or a wax, into a screw feeder or an extruder to form a pre-blend mixture; contacting the pre-blend mixture with water, a surfactant and a neutralizing agent; melt-mixing the mixture; contacting the melt-mixed mixture with additional water at a plurality of subsequent intervals to form an emulsion; and continuously recovering latex particles having low coarse content.
- plasticizer such as a solvent or a wax
- the present disclosure also provides a continuous process which includes co-feeding a polyester and a neutralization agent into a screw feeder or extruder to form a pre-blend mixture; contacting the pre-blend mixture with a plasticizer, water and a surfactant; melt-mixing the mixture; contacting the melt-mixed mixture with additional water at a plurality of subsequent intervals to form an emulsion; and continuously recovering latex particles having low coarse content.
- the present disclosure provides a continuous process which includes feeding a polyester into a screw feeder or extruder; contacting the polyester with a plasticizer, water and a surfactant; melt-mixing the mixture; contacting the melt-mixed mixture with additional water at a plurality of subsequent intervals to form an emulsion; and continuously recovering latex particles having low coarse content.
- the latex may be distilled to remove residual solvent in the latex.
- the resins may be an amorphous resin, a crystalline resin, and/or a combination thereof.
- the resin may be a polyester resin, including the resins described in U.S. Pat. Nos. 6,593,049 and 6,756,176, the disclosures of each of which are hereby incorporated by reference in their entirety. Suitable resins may also include a mixture of an amorphous polyester resin and a crystalline polyester resin as described in U.S. Pat. No. 6,830,860, the disclosure of which is hereby incorporated by reference in its entirety.
- the resin may be a polyester resin formed by reacting a diol with a diacid in the presence of an optional catalyst.
- suitable organic diols include aliphatic diols with from about 2 to about 36 carbon atoms, such as 1,2-ethanedial, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and the like, including their structural isomers.
- the aliphatic diol may be, for example, utilized in an amount of from about 40 to about 60 mole percent, in embodiments from about 42 to about 55 mole percent, in embodiments from about 45 to about 53 mole percent, and a second diol can be utilized in an amount of from about 0 to about 10 mole percent, in embodiments from about 1 to about 4 mole percent of the resin.
- organic diacids or diesters including vinyl diacids or vinyl diesters selected for the preparation of the crystalline resins
- examples of organic diacids or diesters including vinyl diacids or vinyl diesters selected for the preparation of the crystalline resins include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, dimethyl fumarate, dimethyl itaconate, cis, 1,4-diacetoxy-2-butene, diethyl fumarate, diethyl maleate, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexane dicarboxylic acid, malonic acid and mesaconic acid, a diester or anhydride thereof.
- the organic diacid may be utilized in an amount of, for example, in embodiments from about 40 to about 60 mole percent, in embodiments from about 42 to about 52 mole percent, in embodiments from about 45 to about 50 mole percent, and a second diacid can be utilized in an amount of from about 0 to about 10 mole percent of the resin.
- crystalline resins include polyesters, polyamides, polyimides, polyolefins, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polypropylene, mixtures thereof, and the like.
- Specific crystalline resins may be polyester based, such as poly(ethylene-adipate), polypropylene-adipate), poly(butylene-adipate), poly(pentylene-adipate), poly(hexylene-adipate), poly(octylene-adipate), poly(ethylene-succinate), polypropylene-succinate), poly(butylene-succinate), poly(pentylene-succinate), poly(hexylene-succinate), poly(octylene-succinate), poly(ethylene-sebacate), poly(propylene-sebacate), poly(butylene-sebacate), poly(pentylene-sebacate), poly(hexylene-sebacate), poly(octylene-sebacate), poly(decylene-sebacate), poly(decylene-decanoate), poly(ethylene-decanoate), poly(ethylene dodecanoate), poly(nonylene-se
- polyamides examples include poly(ethylene-adipamide), poly(propylene-adipamide), poly(butylenes-adipamide), poly(pentylene-adipamide), poly(hexylene-adipamide), poly(octylene-adipamide), poly(ethylene-succinimide), and poly(propylene-sebecamide).
- polyimides examples include poly(ethylene-adipimide), poly(propylene-adipimide), poly(butylene-adipimide), poly(pentylene-adipimide), poly(hexylene-adipimide), poly(octylene-adipimide), poly(ethylene-succinimide), poly(propylene-succinimide), and poly(butylene-succinimide).
- the crystalline resin may be present, for example, in an amount of from about 1 to about 50 percent by weight of the toner components, in embodiments from about 5 to about 35 percent by weight of the toner components.
- the crystalline resin can possess various melting points of, for example, from about 30° C. to about 120° C., in embodiments from about 50° C. to about 90° C.
- the crystalline resin may have a number average molecular weight (M n ), as measured by gel permeation chromatography (GPC) of, for example, from about 1,000 to about 50,000, in embodiments from about 2,000 to about 25,000, and a weight average molecular weight (M w ) of, for example, from about 2,000 to about 100,000, in embodiments from about 3,000 to about 80,000, as determined by Gel Permeation Chromatography using polystyrene standards.
- M w /M n ) of the crystalline resin may be, for example, from about 2 to about 6, in embodiments from about 3 to about 4.
- diacids or diesters including vinyl diacids or vinyl diesters utilized for the preparation of amorphous polyesters
- dicarboxylic acids or diesters such as terephthalic acid, phthalic acid, isophthalic acid, fumaric acid, trimellitic acid, dimethyl fumarate, dimethyl itaconate, cis, 1,4-diacetoxy-2-butene, diethyl fumarate, diethyl maleate, maleic acid, succinic acid, itaconic acid, succinic acid, succinic anhydride, dodecenylsuccinic acid, dodecenylsuccinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanediacid, dimethyl terephthalate, diethyl terephthalate, dimethylisophthalate, diethylisophthalate, dimethylphthalate, phthalic
- the organic diacids or diesters may be present, for example, in an amount from about 40 to about 60 mole percent of the resin, in embodiments from about 42 to about 52 mole percent of the resin, in embodiments from about 45 to about 50 mole percent of the resin.
- the amount of organic diols selected can vary, and may be present, for example, in an amount from about 40 to about 60 mole percent of the resin, in embodiments from about 42 to about 55 mole percent of the resin, in embodiments from about 45 to about 53 mole percent of the resin.
- suitable amorphous resins include polyesters, polyamides, polyimides, polyolefins, polyethylene, polybutylene, polyisobutyrate, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, polypropylene, combinations thereof, and the like.
- Polycondensation catalysts which may be utilized in forming either the crystalline or amorphous polyesters include tetraalkyl titanates, dialkyltin oxides such as dibutyltin oxide, tetraalkyltins such as dibutyltin dilaurate, and dialkyltin oxide hydroxides such as butyltin oxide hydroxide, aluminum alkoxides, alkyl zinc, dialkyl zinc, zinc oxide, stannous oxide, or combinations thereof.
- Such catalysts may be utilized in amounts of, for example, from about 0.01 mole percent to about 5 mole percent based on the starting diacid or diester used to generate the polyester resin.
- an unsaturated amorphous polyester resin may be utilized as a latex resin.
- examples of such resins and processes for their production include those disclosed in U.S. Pat. No. 6,063,827, the disclosure of which is hereby incorporated by reference in its entirety.
- Exemplary unsaturated amorphous polyester resins include, but are not limited to, poly(propoxylated bisphenol co-fumarate), poly(ethoxylated bisphenol co-fumarate), poly(butyloxylated bisphenol co-fumarate), poly(co-propoxylated bisphenol co-ethoxylated bisphenol co-fumarate), poly(1,2-propylene fumarate), poly(propoxylated bisphenol co-maleate), poly(ethoxylated bisphenol co-maleate), poly(butyloxylated bisphenol co-maleate), poly(co-propoxylated bisphenol co-ethoxylated bisphenol co-maleate), poly(1,2-propylene maleate), poly(propoxylated bisphenol co-itaconate), poly(ethoxylated bisphenol co-itaconate), poly(butyloxylated bisphenol co-itaconate), poly(co-propoxylated bisphenol co-ethoxylated bisphenol co-itaconate
- a suitable polyester resin may be an amorphous polyester such as a poly(propoxylated bisphenol A co-fumarate) resin having the following formula (I):
- m may be from about 5 to about 1000.
- a suitable polyester resin may be an amorphous polyester such as a poly(co-propoxylated bisphenol A co-ethoxylated bisphenol A co-terephthalate co-fumarate co-dodecenylsuccinate) and a branched amorphous polyester such as a poly(co-propoxylated bisphenol A co-ethoxylated bisphenol A co-terephthalate co-dodecenylsuccinate co-trimellitate).
- amorphous polyester such as a poly(co-propoxylated bisphenol A co-ethoxylated bisphenol A co-terephthalate co-fumarate co-dodecenylsuccinate)
- a branched amorphous polyester such as a poly(co-propoxylated bisphenol A co-ethoxylated bisphenol A co-terephthalate co-dodecenylsuccinate co-trimellitate).
- linear propoxylated bisphenol A fumarate resin which may be utilized as a latex resin is available under the trade name SPARII from Resana S/A Industrias Quimicas, Sao Paulo Brazil.
- suitable linear resins include those disclosed in U.S. Pat. Nos. 4,533,614, 4,957,774 and 4,533,614, which can be linear polyester resins including dodecenylsuccinic anhydride, terephthalic acid, and alkyloxylated bisphenol A, the disclosures of which are hereby incorporated by reference in their entirety.
- propoxylated bisphenol A terephthalate resins that may be utilized and are commercially available include GTU-FC115, commercially available from Kao Corporation, Japan, and the like.
- Suitable crystalline resins which may be utilized, optionally in combination with an amorphous resin as descried above, include those disclosed in U.S. Patent Application Publication No. 2006/0222991, the disclosure of which is hereby incorporated by reference in its entirety.
- a suitable crystalline resin may include a resin formed of ethylene glycol and a mixture of dodecanedioic acid and fumaric acid co-monomers with the following formula:
- a suitable crystalline resin may include a resin formed from dodecandioic acid and 1,9-nonanediol monomers.
- a poly(propoxylated bisphenol A co-fumarate) resin of formula I as described above may be combined with a crystalline resin of formula II to form a latex emulsion.
- the amorphous resin may be present, for example, in an amount of from about 30 to about 90 percent by weight of the toner components, in embodiments from about 40 to about 80 percent by weight of the toner components.
- the amorphous resin or combination of amorphous resins utilized in the latex may have a glass transition temperature of from about 30° C. to about 80° C., in embodiments from about 35° C. to about 70° C.
- the combined resins utilized in the latex may have a melt viscosity of from about 10 to about 1,000,000 Pa*S at about 130° C., in embodiments from about 50 to about 100,000 Pa*S.
- the resins may be in any suitable ratio (e.g., weight ratio) such as for instance of from about 1% (first resin)/99% (second resin) to about 99% (first resin)/1% (second resin), in embodiments from about 10% (first resin)/90% (second resin) to about 90% (first resin)/10% (second resin), Where the resin includes an amorphous resin and a crystalline resin, the weight ratio of the two resins may be from about 99% (amorphous resin):1% (crystalline resin), to about 1% (amorphous resin):90% (crystalline resin).
- the resin may possess acid groups which, in embodiments, may be present at the terminal of the resin.
- Acid groups which may be present include carboxylic acid groups, and the like. The number of carboxylic acid groups may be controlled by adjusting the materials utilized to form the resin and reaction conditions.
- the resin may be a polyester resin having an acid number from about 2 mg KOH/g of resin to about 200 mg KOH/g of resin, in embodiments from about 5 mg KOH/g of resin to about 50 mg KOH/g of resin.
- the acid containing resin may be dissolved in a tetrahydrofuran solution.
- the acid number may be detected by titration with KOH/methanol solution containing phenolphthalein as an indicator. The acid number may then be calculated based on the equivalent amount of KOH/methanol required to neutralize all the acid groups on the resin identified as the end point of the titration.
- a plasticizer may be added to the resins described above.
- the plasticizer may be used to soften the resin to a viscosity suitable for passage through an extruder.
- the softened resin may be sufficiently viscous so as to not be free-flowing at room temperature, but sufficiently pliable to be mixed by the extruder.
- the complex viscosity of the softened resin sometimes referred to herein, in embodiments, as a pre-blend mixture, may be from about 10 Pa*S to about 1,000 Pa*S at about 130° C., in embodiments, from about 50 Pa*S to about 500 Pa*S.
- the complex viscosity of the resin pre-blend mixture can be measured using any suitable rheometer.
- a 25 mm sample disc can be prepared by molding about 0.5 grams of pre-blend mixture under a pressure of about 10,000 lbs and the complex viscosity response at various temperature and shear rates can be determined using a parallel plate rheometer such as a Rheometric Scientific Corporation Model ARES.
- a suitable plasticizer for the resin may be, for example, an organic solvent. Any suitable organic solvent may be used, including alcohols, esters, ethers, ketones, amines, combinations thereof, and the like, in an amount of, for example, from about 5% by weight to about 100% by weight of the resin, in embodiments, from about 10% by weight to about 50% by weight of the resin.
- suitable organic solvents include alcohols, such as methanol, ethanol, isopropanol, butanol, as well as higher homologs and polyols, such as ethylene glycol, glycerol, sorbitol, and the like; ketones, such as acetone, 2-butanone, 2-pentanone, 3-pentanone, ethyl isopropyl ketone, methyl isobutyl ketone, diisobutyl ketone, and the like; amides, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1,2-dimethyl-2-imidazolidinone, and the like; nitriles, such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, benzonitrile, and the like; ethers, such as ditertbutyl ether, dimethoxyethane, 2-methoxy
- the organic solvent may be immiscible in water and may have a boiling point of from about 30° C. to about 100° C. Any suitable organic solvent noted hereinabove may also be used as a phase or solvent inversion agent, and may be utilized in an amount of from about 1% by weight to about 25% by weight of the resin, in embodiments from about 5% by weight to about 20% by weight of the resin.
- Waxes may also be used as plasticizers for softening the resin.
- the wax may be provided in a wax dispersion, which may include a single type of wax or a mixture of two or more different waxes. When included, the wax may be present in an amount of, for example, from about 1% by weight to about 25% by weight of the resin, in embodiments from about 5% by weight to about 20% by weight of the resin.
- Waxes that may be utilized include waxes having, for example, a weight average molecular weight of from about 500 to about 20,000, in embodiments from about 1,000 to about 10,000.
- Suitable plasticizer waxes include ester waxes obtained from higher fatty acid and higher alcohol, such as stearyl stearate and behenyl behenate; ester waxes obtained from higher fatty acid and monovalent or multivalent lower alcohols, such as butyl stearate, propyl oleate, glyceride monostearate, glyceride distearate, and pentaerythritol tetra behenate; ester waxes obtained from higher fatty acid and multivalent alcohol multimers, such as diethyleneglycol monostearate, dipropyleneglycol distearate, diglyceryl distearate, and triglyceryl tetrastearate; sorbitan higher fatty acid ester waxes, such as sorbitan monostearate
- plasticizer waxes include functionalized waxes having amines, amides, for example AQUA SUPERSLIP 6550TM, SUPERSLIP 6530TM available from Micro Powder Inc., fluorinated waxes, for example POLYFLUO 190TM, POLYFLUO 200TM, POLYSILK 19TM, POLYSILK 14TM available from Micro Powder Inc., mixed fluorinated and amide waxes, such as aliphatic polar amide functionalized waxes; aliphatic waxes including esters of hydroxylated unsaturated fatty acids, for example MICROSPERSION 19TM available from Micro Powder Inc., imides, esters, quaternary amines, carboxylic acids or acrylic polymer emulsions, for example JONCRYL 74TM, 89TM, 130TM, 537TM, and 538TM, all available from SC Johnson Wax, and chlorinated polypropylenes and polyethylenes, available from Allied Chemical, Petrolite Corporation, and/or SC Johnson wax.
- a crystalline polyester resin may also be used as a plasticizer, which lowers the softening temperature of the amorphous resin such that, at temperatures near the boiling point of water, the viscosity of the melt mix is low enough to form an emulsion.
- the resin may be pre-blended with a weak base or neutralizing agent.
- the base may be contacted with the resin as a solid or in an aqueous solution.
- the resin and the neutralizing agent may be simultaneously fed through a co-feeding process, which may accurately control the feed rate of both the base and the resin into the extruder throughout the process, and which may then be melt-mixed followed by emulsification. Utilizing this process allows for control of the base concentration and a more efficient process. Co-feeding may allow for process repeatability and stability, and lower initial start-up waste.
- the neutralizing agent may be used to neutralize acid groups in the resins, so a neutralizing agent herein may also be referred to as a “basic neutralization agent.”
- a neutralizing agent herein may also be referred to as a “basic neutralization agent.”
- Any suitable basic neutralization reagent may be used in accordance with the present disclosure.
- suitable basic neutralization agents may include both inorganic basic agents and organic basic agents. Suitable basic agents may include ammonium hydroxide, potassium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, lithium hydroxide, potassium carbonate, potassium bicarbonate, combinations thereof, and the like.
- Suitable basic agents may also include monocyclic compounds and polycyclic compounds having at least one nitrogen atom, such as, for example, secondary amines, which include aziridines, azetidines, piperazines, piperidines, pyridines, bipyridines, terpyridines, dihydropyridines, morpholines, N-alkylmorpholines, 1,4-diazabicyclo[2.2.2]octanes, 1,8-diazabicycloundecanes, 1,8-diazabicycloundecenes, dimethylated pentylamines, trimethylated pentylamines, pyrimidines, pyrroles, pyrrolidines, pyrrolidinones, indoles, indolines, indanones, benzindazones, imidazoles, benzimidazoles, imidazolones, imidazolines, oxazoles, isoxazoles, oxazolines, o
- the basic agent may be utilized as a solid such as, for example, sodium hydroxide flakes, so that it is present in an amount of from about 0.001% by weight to 50% by weight of the resin, in embodiments from about 0.01% by weight to about 25% by weight of the resin, in embodiments from about 0.1% by weight to 5% by weight of the resin.
- the basic neutralization agent may be added to a resin possessing acid groups.
- the addition of the basic neutralization agent may thus raise the pH of an emulsion including a resin possessing acid groups to a pH of from about 5 to about 12, in embodiments, from about 6 to about 11.
- the neutralization of the acid groups may, in embodiments, enhance formation of the emulsion.
- the process of the present disclosure may include adding a surfactant, before or during the melt-mixing, to the resin at an elevated temperature.
- a solid surfactant may be co-fed with the resin and the neutralizing agent into the extruder.
- a solid surfactant may be added to the resin and the neutralizing agent to form a pre-blend mixture prior to melt-mixing.
- a resin emulsion may include one, two, or more surfactants.
- the surfactants may be selected from ionic surfactants and nonionic surfactants.
- anionic surfactants and cationic surfactants are encompassed by the term “ionic surfactants.”
- the surfactant may be added as a solid or as a solution with a concentration of from about 5% to about 100% (pure surfactant) by weight, in embodiments, from about 10% to about 95% by weight.
- the surfactant may be utilized so that it is present in an amount of from about 0.01% to about 20% by weight of the resin, in embodiments, from about 0.1% to about 16% by weight of the resin, in embodiments, from about 1% to about 14% by weight of the resin.
- Anionic surfactants which may be utilized include sulfates and sulfonates, sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl sulfates and sulfonates, acids such as abitic acid available from Aldrich, NEOGEN RTM, NEOGEN SCTM obtained from Daiichi Kogyo Seiyaku, combinations thereof, and the like.
- SDS sodium dodecylsulfate
- sodium dodecylbenzene sulfonate sodium dodecylnaphthalene sulfate
- dialkyl benzenealkyl sulfates and sulfonates acids such as abitic acid available from Aldrich, NEOGEN RTM, NEOGEN SCTM obtained from Daiichi Kogyo Seiyaku, combinations thereof, and
- anionic surfactants include, in embodiments, DOWFAXTM 2A1, an alkyldiphenyloxide disulfonate from The Dow Chemical Company, and/or TAYCA POWER BN2060 from Tayca Corporation (Japan), which are branched sodium dodecylbenzene sulfonates. Combinations of these surfactants and any of the foregoing anionic surfactants may be utilized in embodiments.
- cationic surfactants which are usually positively charged, include, for example, alkylbenzyl dimethyl ammonium chloride, dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, cetyl pyridinium bromide, C 12 , C 15 , C 17 trimethyl ammonium bromides, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyl triethyl ammonium chloride, MIRAPOLTM and ALKAQUATTM, available from Alkaril Chemical Company, SANIZOLTM (benzalkonium chloride), available from Kao Chemicals, and the like, and mixtures thereof.
- alkylbenzyl dimethyl ammonium chloride dialkyl benzenealkyl ammonium chloride, lauryl trimethyl am
- nonionic surfactants that may be utilized for the processes illustrated herein include, for example, polyvinyl alcohol, polyacrylic acid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxy poly(ethyleneoxy)ethanol, available from Rhone-Poulenc as IGEPAL CA-210TM, IGEPAL CA-520TM, IGEPAL CA-720TM, IGEPAL CO-890TM, IGEPAL CO-720TM, IGEPAL CO-290TM, IGEPAL CA-210TM, ANTAROX 890TM and ANTARO
- nonionic surfactants may include a block copolymer of polyethylene oxide and polypropylene oxide, including those commercially available as SYNPERONIC PE/F, in embodiments SYNPERONIC PE/F 108 . Combinations of these surfactants and any of the foregoing surfactants may be utilized in embodiments.
- the present continuous process includes melt-mixing a mixture in an extruder at an elevated temperature containing a resin possessing acid groups, a solvent or a plasticizer, and a solid or aqueous surfactant, and a neutralizing agent.
- the elevated temperature may be from about 30° C. to about 200° C., in embodiments from about 50° C. to about 150° C., in embodiments from about 70° C. to about 100° C.
- the solvent-assisted extruder process of the present disclosure may be accomplished via a system as shown in the FIGURE.
- the disclosed process reduces degradation of polyster resins when compared to the solventless processes.
- Melt-mixing of the resin may be conducted in an extruder 30 , which may be a twin screw extruder, a kneader such as a Haake mixer, a batch reactor, or any other device capable of intimately mixing viscous materials to create near homogenous mixtures.
- Stirring although not necessary, may be utilized to enhance formation of the latex. Any suitable stirring device may be utilized.
- the stirring may be at from about 10 revolutions per minute (rpm) to about 5,000 rpm, in embodiments from about 20 rpm to about 2,000 rpm, in embodiments from about 50 rpm to about 1,000 rpm.
- the stirring need not be at a constant speed and may be varied. For example, as the heating of the mixture becomes more uniform, the stirring rate may be increased.
- the resin may be an amorphous resin, a crystalline resin, or a combination thereof.
- the resin may be an amorphous resin and the elevated temperature may be a temperature above the glass transition temperature of the amorphous resin.
- the resin may be a crystalline resin and the elevated temperature may be a temperature above the melting point of the crystalline resin.
- the resin may be a mixture of amorphous and crystalline resins and the temperature may be above the glass transition temperature of the mixture.
- the resin, the plasticizer and the neutralizing agent may be pre-blended prior to melt-mixing.
- the resin and the plasticizer may be mixed in a tumbler 10 for from about 10 minutes to about 60 minutes, in embodiments from about 15 minutes to about 30 minutes, at a rotor speed of from about 1 rotation per minute (rpm) to about 20 rpm, in embodiments from about 5 rpm to about 15 rpm, to prepare a pre-blend mixture.
- the pre-blend resin mixture is fed through a screw feeder 20 coupled to the extruder 30 .
- the pre-blend resin mixture may be co-fed into the extruder 30 with the neutralizing agent in solid form, such as flakes or pellets being fed through a separate feeder (not shown).
- the neutralizing agent may be used in an aqueous solution, the dissolved neutralizing agent may be pre-mixed with the surfactant and water in a vessel 45 and co-fed through pump 55 to extruder injection port 75 or fed separately to injection port 75 .
- the neutralizing agent may be fed at a rate such that it is at a concentration of about 0.2% by weight to about 5% by weight of the resin, in embodiments, from about 0.4% by weight to about 2% by weight of the resin. Concentration of the components is provided rather than the rates to achieve the desired composition since flow and feed rates vary with the scale of the processing equipment (e.g., extruder 30 ).
- a solid surfactant may be utilized and co-fed with the resin into the extruder feed hopper.
- the surfactant may be added to the resin composition before, during, or after melt-mixing and before, during, or after the addition of the neutralizing agent.
- the surfactant may be in an aqueous solution. More specifically, as the pre-blend resin mixture travels down the extruder 30 , a solution of the surfactant may be fed into the extruder's injection port 75 , from the vessel 45 via the diaphragm pump 55 and heated via heat exchanger 65 .
- the water in the surfactant solution activates the neutralizing agent while the surfactant is melt-mixed with the resin to produce a homogeneous mixture of a neutralized resin.
- the surfactant is fed at a rate such that it is at a concentration of about 0.5% by weight to about 20% by weight of the resin, in embodiments, from about 2% by weight to about 15% by weight of the resin.
- the plasticizer may be injected directly into the extruder 30 to blend the resin and the plasticizer within the extruder 30 , thus eliminating the need for pre-blending.
- the plasticizer may be fed through an extruder injection port 70 , from a vessel 40 via a diaphragm pump 50 and heated via heat exchanger 60 .
- the plasticizer may be injected at a rate such that it is at a concentration of about 5% by weight to about 100% by weight of the resin, in embodiments, from about 10% by weight to about 50% by weight of the resin.
- the injection port 70 may be disposed at a first section I of the extruder 30 , which acts as a melting zone, prior to the injection port 75 , which supplies the surfactant solution.
- the injection port 75 may be disposed at a second section II subsequent to the first section, such that the surfactant is added to the mixture after the plasticizer has been mixed with the resin in the extruder 30 .
- the injection ports 70 and 75 may be disposed at the same section, e.g., first section, in the extruder 30 such that the plasticizer and surfactant are fed simultaneously.
- the melt-mixed water in oil dispersion mixture may then be phase inverted with additional water, to form an oil in water latex emulsion.
- De-ionized water DIW
- water temperatures may be from about 20° C. to about 110° C., in embodiments, from about 60° C. to about 100° C.
- DIW may be added at three subsequent ports 110 , 140 , and 170 at section III of the extruder 30 .
- DIW may be stored in a tank 80 and be fed to the extruder's injection port 110 , injection port 140 , via diaphragm pumps 90 , 120 , and 150 .
- the DIW is heated via heat exchangers 100 , 130 , and 160 , respectively.
- the ports may inject preheated de-ionized water into the extruder at rates of from about 40 g/min to about 400 g/min, in embodiments, of from about 100 g/min to about 200 g/min, such that the final solids content of the latex is from about 10% to about 40%, in embodiments, from about 15% to about 35%.
- the product exiting from the extruder may include a stream of latex that is collected in a steam traced tank 200 with gentle agitation with additional DIW fed from tank 80 to achieve the desired final product solids content, via diaphragm pump 180 and heated via heat exchanger 190 .
- a desired latex is achieved, the latex is discharged as a latex stream 210 for storage and later use in the aggregation/coalescence process described below.
- the particle size of the latex emulsion formed can be controlled by the concentration ratio of plasticizer, surfactant, neutralizing agent to polyester resin.
- the solids concentration of the latex may be controlled by the ratio of the resin mixture to the water.
- the processes herein may produce emulsified resin particles that retain the same molecular weight properties of the starting resin, in embodiments, the pre-made resins utilized in forming the emulsion.
- the emulsified resin particles in the aqueous medium may have a size of about 1500 nm or less, such as from about 10 nm to about 1200 nm, in embodiments from about 30 nm to about 1,000 nm.
- Particle size distribution of a latex of the present disclosure may be from about 60 nm to about 300 nm, in embodiments, from about 125 nm to about 200 nm.
- the coarse content of the latex of the present disclosure may be from about 0% by weight to about 1% by weight, in embodiments, from about 0.1% by weight to about 0.5% by weight.
- the solids content of the latex of the present disclosure may be from about 5% by weight to about 50% by weight, in embodiments, from about 30% by weight to about 40% by weight.
- emulsification Following emulsification, additional surfactant, water, and/or neutralizing agent may optionally be added to dilute the emulsion, although this is not required. Following emulsification, the emulsion may be cooled to room temperature, for example from about 20° C. to about 25° C. Following emulsification the latex may be distilled to remove residual solvent in the latex.
- the latex emulsions of the present disclosure offer several advantages including, for example, low coarse content; tight particle size distributions and particle sizes appropriate for emulsion aggregation toner manufacturing; no homogenizers or other dispersing devices required for the preparation of latexes; no filtration to eliminate coarse particles; and latex production on demand from a convenient solid material.
- the latex emulsions of the present disclosure may then be utilized to produce particle sizes that are suitable for ultra low melt emulsion aggregation processes, using crystalline and/or amorphous polyester resins.
- the latexes may be produced with a low coarse content without the use of homogenization or filtration.
- the resulting latex may then be utilized to form a toner by any method within the purview of those skilled in the art.
- the latex emulsion may be contacted with a colorant, optionally in a dispersion, and other additives to form an ultra low melt toner by a suitable process, in embodiments, an emulsion aggregation and coalescence process.
- the optional additional ingredients of a toner composition may also be added before, during or after melt-mixing the resin to form the latex emulsion of the present disclosure.
- the additional ingredients may be added before, during or after formation of the latex emulsion.
- the colorant may be added before the addition of the surfactant.
- the colorant to be added various known suitable colorants, such as dyes, pigments, mixtures of dyes, mixtures of pigments, mixtures of dyes and pigments, and the like, may be included in the toner.
- the colorant may be included in the toner in an amount of, for example, about 0.1 to about 35% by weight of the toner, or from about 1 to about 15% by weight of the toner, or from about 3 to about 10% by weight of the toner, although the amount of colorant can be outside of these ranges.
- suitable colorants include carbon black like REGAL 330® (Cabot), Carbon Black 5250 and 5750 (Columbian Chemicals), Sunsperse Carbon Black LHD 9303 (Sun Chemicals); magnetites, such as Mobay magnetites MO8029TM, MO8060TM; Columbian magnetites; MAPICO BLACKSTM and surface treated magnetites; Pfizer magnetites CB4799TM, CB5300TM, CB5600TM, MCX6369TM; Bayer magnetites, BAYFERROX 8600TM, 8610TM; Northern Pigments magnetites, NP-604TM, NP-608TM; Magnox magnetites TMB-100TM, or TMB-104TM; and the like.
- magnetites such as Mobay magnetites MO8029TM, MO8060TM; Columbian magnetites; MAPICO BLACKSTM and surface treated magnetites; Pfizer magnetites CB4799TM, CB5300TM, CB5600TM, MCX6369TM; Bayer magnetites, BAYFERROX 8600TM, 8610
- colored pigments there can be selected cyan, magenta, yellow, red, green, brown, blue or mixtures thereof. Generally, cyan, magenta, or yellow pigments or dyes, or mixtures thereof, are used. The pigment or pigments are generally used as water based pigment dispersions.
- suitable colorants may include Paliogen Violet 5100 and 5890 (BASF), Normandy Magenta RD-2400 (Paul Uhlrich), Permanent Violet VT2645 (Paul Uhlrich), Heliogen Green L8730 (BASF), Argyle Green XP-111-S (Paul Uhlrich), Brilliant Green Toner GR 0991 (Paul Uhlrich), Lithol Scarlet D3700 (BASF), Toluidine Red (Aldrich), Scarlet for Thermoplast NSD PS PA (Ugine Kuhlmann of Canada), Lithol Rubine Toner (Paul Uhlrich), Lithol Scarlet 4440 (BASF), NBD 3700 (BASF), Bon Red C (Dominion Color), Royal Brilliant Red RD-8192 (Paul Uhlrich), Oracet Pink RF (Ciba Geigy), Paliogen Red 3340 and 3871K (BASF), Lithol Fast Scarlet L4300 (BASF), Heliogen Blue D6840, D7080, K7090, K6910
- Suitable water based colorant dispersions include those commercially available from Clariant, for example, Hostafine Yellow GR, Hostafine Black T and Black TS, Hostafine Blue B2G, Hostafine Rubine F6B and magenta dry pigment such as Toner Magenta 6BVP2213 and Toner Magenta EO2 which may be dispersed in water and/or surfactant prior to use.
- pigments include Sunsperse BHD 6011X (Blue 15 Type), Sunsperse BHD 9312X (Pigment Blue 15 74160), Sunsperse BHD 6000X (Pigment Blue 15:3 74160), Sunsperse GHD 9600X and GHD 6004X (Pigment Green 7 74260), Sunsperse QHD 6040X (Pigment Red 122 73915), Sunsperse RHD 9668X (Pigment Red 185 12516), Sunsperse RHD 9365X and 9504X (Pigment Red 57 15850:1, Sunsperse YHD 6005X (Pigment Yellow 83 21108), Flexiverse YFD 4249 (Pigment Yellow 17 21105), Sunsperse YHD 6020X and 6045X (Pigment Yellow 74 11741), Sunsperse YHD 600X and 9604X (Pigment Yellow 14 21095), Flexiverse LFD 4343 and
- colorants that can be selected are black, cyan, magenta, or yellow, and mixtures thereof.
- magentas are 2,9-dimethyl-substituted quinacridone and anthraquinone dye identified in the Color Index as CI 60710, CI Dispersed Red 15, diazo dye identified in the Color Index as CI 26050, CI Solvent Red 19, and the like.
- cyans include copper tetra(octadecyl sulfonamido) phthalocyanine, x-copper phthalocyanine pigment listed in the Color Index as CI 74160, CI Pigment Blue, Pigment Blue 15:3, and Anthrathrene Blue, identified in the Color Index as CI 69810, Special Blue X-2137, and the like.
- yellows are diarylide yellow 3,3-dichlorobenzidene acetoacetanilides, a monoazo pigment identified in the Color Index as CI 12700, CI Solvent Yellow 16, a nitrophenyl amine sulfonamide identified in the Color Index as Foron Yellow SE/GLN, CI Dispersed Yellow 33 2,5-dimethoxy-4-sulfonanilide phenylazo-4′-chloro-2,5-dimethoxy acetoacetanilide, and Permanent Yellow FGL.
- the colorant may include a pigment, a dye, combinations thereof, carbon black, magnetite, black, cyan, magenta, yellow, red, green, blue, brown, combinations thereof, in an amount sufficient to impart the desired color to the toner. It is to be understood that other useful colorants will become readily apparent based on the present disclosures.
- a pigment or colorant may be employed in an amount of from about 1% by weight to about 35% by weight of the toner particles on a solids basis, in embodiments, from about 5% by weight to about 25% by weight. However, amounts outside these ranges can also be used, in embodiments.
- a wax may also be combined with the resin and a colorant in forming toner particles.
- the wax may be provided in a wax dispersion, which may include a single type of wax or a mixture of two or more different waxes.
- a single wax may be added to toner formulations, for example, to improve particular toner properties, such as toner particle shape, presence and amount of wax on the toner particle surface, charging and/or fusing characteristics, gloss, stripping, offset properties, and the like.
- a combination of waxes can be added to provide multiple properties to the toner composition.
- the wax may be present in an amount of, for example, from about 1% by weight to about 25% by weight of the toner particles, in embodiments from about 5% by weight to about 20% by weight of the toner particles, although the amount of wax can be outside of these ranges.
- the wax dispersion may include any of the various waxes conventionally used in emulsion aggregation toner compositions.
- Waxes that may be selected include waxes having, for example, an average molecular weight of from about 500 to about 20,000, in embodiments from about 1,000 to about 10,000.
- Waxes that may be used include, for example, polyolefins such as polyethylene including linear polyethylene waxes and branched polyethylene waxes, polypropylene including linear polypropylene waxes and branched polypropylene waxes, polyethylene/amide, polyethylenetetrafluoroethylene, polyethylenetetrafluoroethylene/amide, and polybutene waxes such as commercially available from Allied Chemical and Petrolite Corporation, for example POLYWAXTM polyethylene waxes such as commercially available from Baker Petrolite, wax emulsions available from Michaelman, Inc.
- polyolefins such as polyethylene including linear polyethylene waxes and branched polyethylene waxes
- polypropylene including linear polypropylene waxes and branched polypropylene waxes polyethylene/amide
- polyethylenetetrafluoroethylene polyethylenetetrafluoroethylene/amide
- polybutene waxes such as commercially available from Allied Chemical and Petrolite Corporation
- EPOLENE N-15TM commercially available from Eastman Chemical Products, Inc.
- VISCOL 550PTM a low weight average molecular weight polypropylene available from Sanyo Kasei K. K.
- plant-based waxes such as carnauba wax, rice wax, candelilla wax, sumacs wax, and jojoba oil
- animal-based waxes such as beeswax
- mineral-based waxes and petroleum-based waxes such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax such as waxes derived from distillation of crude oil, silicone waxes, mercapto waxes, polyester waxes, urethane waxes
- modified polyolefin waxes such as a carboxylic acid-terminated polyethylene wax or a carboxylic acid-terminated polypropylene wax
- Fischer-Tropsch wax ester waxes obtained from higher fatty acid and higher alcohol, such as steadiol,
- Examples of functionalized waxes that may be used include, for example, amines, amides, for example AQUA SUPERSLIP 6550TM, SUPERSLIP 6530TM available from Micro Powder Inc., fluorinated waxes, for example POLYFLUO 190TM, POLYFLUO 200TM, POLYSILK 19TM, POLYSILK 14TM available from Micro Powder Inc., mixed fluorinated, amide waxes, such as aliphatic polar amide functionalized waxes; aliphatic waxes consisting of esters of hydroxylated unsaturated fatty acids, for example MICROSPERSION 19TM also available from Micro Powder Inc., imides, esters, quaternary amines, carboxylic acids or acrylic polymer emulsion, for example JONCRYL 74TM, 89TM, 130TM, 537TM, and 538TM, all available from SC Johnson Wax, and chlorinated polypropylenes and polyethylenes available from Allied Chemical and Petrolite Corporation and SC Johnson wax
- the wax may be incorporated into the toner in the form of one or more aqueous emulsions or dispersions of solid wax in water, where the solid wax particle size may be of from about 100 nm to about 300 nm, in embodiments from about 125 nm to about 275 nm.
- the toner particles may be prepared by any method within the purview of one skilled in the art. Although embodiments relating to toner particle production are described below with respect to emulsion aggregation processes, any suitable method of preparing toner particles may be used, including chemical processes, such as suspension and encapsulation processes disclosed in U.S. Pat. Nos. 5,290,654 and 5,302,486, the disclosures of each of which are hereby incorporated by reference in their entirety. In embodiments, toner compositions and toner particles may be prepared by aggregation and coalescence processes in which small-size resin particles are aggregated to the appropriate toner particle size and then coalesced to achieve the final toner particle shape and morphology.
- toner compositions may be prepared by emulsion aggregation processes, such as a process that includes aggregating a mixture of an optional colorant, an optional wax and any other desired or required additives, and emulsions including the resins described above, optionally in surfactants as described above, and then coalescing the aggregate mixture.
- a mixture may be prepared by adding a colorant and optionally a wax or other materials, which may also be optionally in a dispersion(s) including a surfactant, to the emulsion, which may be a mixture of two or more emulsions containing the resin.
- the pH of the resulting mixture may be adjusted by an acid such as, for example, acetic acid, nitric acid or the like.
- the pH of the mixture may be adjusted to from about 2 to about 5. Additionally, in embodiments, the mixture may be homogenized. If the mixture is homogenized, homogenization may be accomplished by mixing at about 600 to about 6,000 revolutions per minute. Homogenization may be accomplished by any suitable means, including, for example, an IKA ULTRA TURRAX T50 probe homogenizer.
- an aggregating agent may be added to the mixture. Any suitable aggregating agent may be utilized to form a toner. Suitable aggregating agents include, for example, aqueous solutions of a divalent cation or a multivalent cation material.
- the aggregating agent may be, for example, an inorganic cationic aggregating agent such as polyaluminum halides such as polyaluminum chloride (PAC), or the corresponding bromide, fluoride, or iodide, polyaluminum silicates such as polyaluminum sulfosilicate (PASS), and water soluble metal salts including aluminum chloride, aluminum nitrite, aluminum sulfate, potassium aluminum sulfate, calcium acetate, calcium chloride, calcium nitrite, calcium oxylate, calcium sulfate, magnesium acetate, magnesium nitrate, magnesium sulfate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, magnesium bromide, copper chloride, copper sulfate, and combinations thereof.
- the aggregating agent may be added to the mixture at a temperature that is below the glass transition temperature (Tg) of the resin.
- organic cationic aggregating agents include, for example, dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, cetyl pyridinium bromide, C 12 , C 15 , C 17 trimethyl ammonium bromides, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyl triethyl ammonium chloride, combinations thereof, and the like.
- Suitable aggregating agents also include, but are not limited to, tetraalkyl titanates, dialkyltin oxide, tetraalkyltin oxide hydroxide, dialkyltin oxide hydroxide, aluminum alkoxides, alkylzinc, dialkyl zinc, zinc oxides, stannous oxide, dibutyltin oxide, dibutyltin oxide hydroxide, tetraalkyl tin, combinations thereof, and the like.
- the aggregating agent is a polyion aggregating agent
- the agent may have any desired number of polyion atoms present.
- suitable polyaluminum compounds have from about 2 to about 13, in embodiments, from about 3 to about 8, aluminum ions present in the compound.
- the aggregating agent may be added to the mixture utilized to form a toner in an amount of, for example, from about 0% to about 10% by weight, in embodiments from about 0.2% to about 8% by weight, in embodiments from about 0.5% to about 5% by weight, of the resin in the mixture. This should provide a sufficient amount of agent for aggregation.
- the particles may be permitted to aggregate until a predetermined desired particle size is obtained.
- a predetermined desired size refers to the desired particle size to be obtained as determined prior to formation, and the particle size being monitored during the growth process until such particle size is reached.
- Samples may be taken during the growth process and analyzed, for example with a Coulter Counter, for average particle size.
- the aggregation thus may proceed by maintaining the elevated temperature, or slowly raising the temperature to, for example, from about 40° C. to about 100° C., and holding the mixture at this temperature for a time of from about 0.5 hours to about 6 hours, in embodiments from about hour 1 to about 5 hours, while maintaining stirring, to provide the aggregated particles.
- the growth process is halted.
- the growth and shaping of the particles following addition of the aggregation agent may be accomplished under any suitable conditions.
- the growth and shaping may be conducted under conditions in which aggregation occurs separate from coalescence.
- the aggregation process may be conducted under shearing conditions at an elevated temperature, for example of from about 40° C. to about 90° C., in embodiments from about 45° C. to about 80° C., which may be below the glass transition temperature of the resin as discussed above.
- the pH of the mixture may be adjusted with a base to a value of from about 3 to about 10, and in embodiments from about 5 to about 9.
- the adjustment of the pH may be utilized to freeze, that is to stop, toner growth.
- the base utilized to stop toner growth may include any suitable base such as, for example, alkali metal hydroxides such as, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, combinations thereof, and the like.
- alkali metal hydroxides such as, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, combinations thereof, and the like.
- ethylene diamine tetraacetic acid (EDTA) may be added to help adjust the pH to the desired values noted above.
- a resin coating may be applied to the aggregated particles to form a shell thereover. Any resin described above may be utilized as the shell.
- a polyester amorphous resin latex as described above may be included in the shell.
- the polyester amorphous resin latex described above may be combined with a different resin, and then added to the particles as a resin coating to form a shell.
- resins which may be utilized to form a shell include, but are not limited to, a crystalline resin latex described above, and/or the amorphous resins described above.
- an amorphous resin which may be utilized to form a shell in accordance with the present disclosure includes an amorphous polyester, optionally in combination with a crystalline polyester resin latex described above. Multiple resins may be utilized in any suitable amounts.
- a first amorphous polyester resin for example an amorphous resin of formula I above, may be present in an amount of from about 20 percent by weight to about 100 percent by weight of the total shell resin, in embodiments from about 30 percent by weight to about 90 percent by weight of the total shell resin.
- a second resin may be present in the shell resin in an amount of from about 0 percent by weight to about 80 percent by weight of the total shell resin, in embodiments from about 10 percent by weight to about 70 percent by weight of the shell resin.
- the shell resin may be applied to the aggregated particles by any method within the purview of those skilled in the art.
- the resins utilized to form the shell may be in an emulsion including any surfactant described above.
- the emulsion possessing the resins, optionally the solvent-assisted crystalline polyester resin latex neutralized with NaOH flakes described above, may be combined with the aggregated particles described above so that the shell forms over the aggregated particles.
- the formation of the shell over the aggregated particles may occur while heating to a temperature of from about 30° C. to about 80° C., in embodiments from about 35° C. to about 70° C.
- the formation of the shell may take place for a period of time of from about 5 minutes to about 10 hours, in embodiments from about 10 minutes to about 5 hours.
- the particles may then be coalesced to the desired final shape, the coalescence being achieved by, for example, heating the mixture to a temperature of from about 45° C. to about 100° C., in embodiments from about 55° C. to about 99° C., which may be at or above the glass transition temperature of the resins utilized to form the toner particles, and/or reducing the stirring, for example to from about 100 rpm to about 1,000 rpm, in embodiments from about 200 rpm to about 800 rpm.
- Coalescence may be accomplished over a period of from about 0.01 to about 9 hours, in embodiments from about 0.1 to about 4 hours.
- the mixture may be cooled to room temperature, such as from about 20° C. to about 25° C.
- the cooling may be rapid or slow, as desired.
- a suitable cooling method may include introducing cold water to a jacket around the reactor. After cooling, the toner particles may be optionally washed with water, and then dried. Drying may be accomplished by any suitable method for drying including, for example, freeze-drying.
- the toner particles may also contain other optional additives, as desired or required.
- the toner may include positive or negative charge control agents, for example in an amount of from about 0.1 to about 10% by weight of the toner, in embodiments from about 1 to about 3% by weight of the toner.
- positive or negative charge control agents include quaternary ammonium compounds inclusive of alkyl pyridinium halides; bisulfates; alkyl pyridinium compounds, including those disclosed in U.S. Pat. No. 4,298,672, the disclosure of which is hereby incorporated by reference in its entirety; organic sulfate and sulfonate compositions, including those disclosed in U.S. Pat. No.
- additives can also be blended with the toner particles external additive particles after formation including flow aid additives, which additives may be present on the surface of the toner particles.
- these additives include metal oxides such as titanium oxide, silicon oxide, aluminum oxides, cerium oxides, tin oxide, mixtures thereof, and the like; colloidal and amorphous silicas, such as AEROSIL®, metal salts and metal salts of fatty acids inclusive of zinc stearate, calcium stearate, or long chain alcohols such as UNILIN 700, and mixtures thereof.
- silica may be applied to the toner surface for toner flow, tribo enhancement, admix control, improved development and transfer stability, and higher toner blocking temperature.
- TiO 2 may be applied for improved relative humidity (RH) stability, tribo control and improved development and transfer stability.
- Zinc stearate, calcium stearate and/or magnesium stearate may optionally also be used as an external additive for providing lubricating properties, developer conductivity, tribo enhancement, enabling higher toner charge and charge stability by increasing the number of contacts between toner and carrier particles.
- a commercially available zinc stearate known as Zinc Stearate L obtained from Ferro Corporation, may be used.
- the external surface additives may be used with or without a coating.
- each of these external additives may be present in an amount of from about 0.1% by weight to about 5% by weight of the toner, in embodiments of from about 0.25% by weight to about 3% by weight of the toner, although the amount of additives can be outside of these ranges.
- the toners may include, for example, from about 0.1% by weight to about 5% by weight titania, from about 0.1% by weight to about 8% by weight silica, and from about 0.1% by weight to about 4% by weight zinc stearate.
- Suitable additives include those disclosed in U.S. Pat. Nos. 3,590,000 and 6,214,507, the disclosures of each of which are hereby incorporated by reference in their entirety.
- An extruder equipped with a feed hopper and liquid injection ports is preheated to about 70-80° C. and set to a rotor speed of about 450 rpm.
- About 38.8 grams of NaOH flakes and about 6.46 kilograms of a poly(co-propoxylated bisphenol co-ethoxylated bisphenol co-terephtalate) polyester amorphous resin is mixed in a tumbler for about 15 minutes at a rotor speed of about 15 rpm to prepare a pre-blend mixture.
- the pre-blend mixture is loaded into the hopper of a screw feeder which delivers about 350 g/min of the mixture to the extruder.
- the pre-blend mixture melts as it travels down the screw feeder.
- a mixture of methyl ethyl ketone (MEK) and water (9:1 w/w) is preheated to a temperature of about 55° C. via a heat exchanger and is fed to the extruder's first injection port at a feed rate of about 350 g/min via a diaphragm pump.
- the water in the solution activates the NaOH, while the solvent dissolves the melted mixture, which combine to form a homogeneous mixture of neutralized resin in solvent and water.
- DIW deionized water
- the product from the extruder is collected in a tank with gentle agitation to which additional DIW is added at a feed rate of about 81 g/min via a diaphragm pump and is heated via a heat exchanger. This product is then transferred to a batch distillation system where the MEK is distilled off of the latex to yield a latex with less than 400 ppm of MEK.
- An extruder equipped with a feed hopper and liquid injection ports is preheated to about 70-80° C. and set to a rotor speed of about 450 rpm.
- About 50 grams of piperazine powder and about 6.46 kilograms of a poly(co-propoxylated bisphenol co-ethoxylated bisphenol co-terephtalate) polyester amorphous resin is mixed in a tumbler for about 15 minutes at a rotor speed of about 15 rpm to prepare a pre-blend mixture.
- This pre-blend mixture is then loaded into the hopper of a screw feeder which delivers about 350 g/min of the mixture to the extruder.
- the pre-blend mixture melts as it travels down the screw feeder.
- Methyl ethyl ketone is preheated to a temperature of about 55° C. via a heat exchanger and is fed to the extruder's first injection port at a feed rate of about 350 g/min via a diaphragm pump.
- the piperazine neutralizes the acid end groups on the resin, while the solvent dissolves the melt, which combine to form a homogeneous mixture of neutralized resin in solvent.
- DIW is added at three subsequent ports. DIW is fed to the extruder's second injection port, third injection port, and fourth injection port, at feed rates of about 89 g/min, about 190 g/min, and about 110 g/min, respectively, via diaphragm pumps, and is heated via heat exchangers.
- the addition of water at these rates provides for a gradual transition from a water in oil to an oil in water emulsion ensuring that the material continues to mix rather than phase separate.
- the product from the extruder is collected in a tank with gentle agitation to which additional DIW is added at a feed rate of 81 g/min via a diaphragm pump and heated via a heat exchanger. This product is then transferred to a batch distillation system where the MEK is distilled off of the latex to yield a latex with less than 400 ppm of MEK.
Abstract
Description
wherein b is from about 5 to about 2000 and d is from about 5 to about 2000. In embodiments, a suitable crystalline resin may include a resin formed from dodecandioic acid and 1,9-nonanediol monomers.
Claims (20)
Priority Applications (4)
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US12/819,462 US8168699B2 (en) | 2010-06-21 | 2010-06-21 | Solvent-assisted continuous emulsification processes for producing polyester latexes |
JP2011127704A JP5687139B2 (en) | 2010-06-21 | 2011-06-07 | Continuous emulsification process using solvent to produce polyester latex |
CA2743155A CA2743155C (en) | 2010-06-21 | 2011-06-14 | Solvent-assisted continuous emulsification processes for producing polyester latexes |
RU2011124159/04A RU2011124159A (en) | 2010-06-21 | 2011-06-15 | METHOD FOR CONTINUOUS EMULGING UNDER SOLVENT ASSISTANCE FOR PRODUCTION OF POLYESTER LATEX |
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US12/819,462 US8168699B2 (en) | 2010-06-21 | 2010-06-21 | Solvent-assisted continuous emulsification processes for producing polyester latexes |
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US20110313079A1 US20110313079A1 (en) | 2011-12-22 |
US8168699B2 true US8168699B2 (en) | 2012-05-01 |
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US12/819,462 Active US8168699B2 (en) | 2010-06-21 | 2010-06-21 | Solvent-assisted continuous emulsification processes for producing polyester latexes |
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US (1) | US8168699B2 (en) |
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US20140200298A1 (en) * | 2013-01-14 | 2014-07-17 | Xerox Corporation | Toner making process |
US8871420B1 (en) | 2013-04-10 | 2014-10-28 | Xerox Corporation | Method and system for magnetic actuated mixing to prepare latex emulsion |
US8932792B2 (en) | 2012-11-27 | 2015-01-13 | Xerox Corporation | Preparation of polyester latex emulsification by direct steam injection |
US20150086922A1 (en) * | 2013-09-24 | 2015-03-26 | Xerox Corporation | Latex forming process comprising concurrent steam injection emulsification and solvent distillation |
US9090760B2 (en) | 2013-04-04 | 2015-07-28 | Xerox Corporation | Continuous latex production processes |
US9234090B2 (en) | 2013-04-10 | 2016-01-12 | Xerox Corporation | Method and system for magnetic actuated milling for pigment dispersions |
US9243148B2 (en) | 2013-03-29 | 2016-01-26 | Xerox Corporation | Preparation of pigment dispersions and toner compositions |
US9261801B2 (en) * | 2014-04-04 | 2016-02-16 | Xerox Corporation | Steam injection process for preparing polyester latex and apparatus thereof |
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US8932792B2 (en) | 2012-11-27 | 2015-01-13 | Xerox Corporation | Preparation of polyester latex emulsification by direct steam injection |
US20140200298A1 (en) * | 2013-01-14 | 2014-07-17 | Xerox Corporation | Toner making process |
US8858896B2 (en) * | 2013-01-14 | 2014-10-14 | Xerox Corporation | Toner making process |
DE102014200371B4 (en) * | 2013-01-14 | 2018-11-15 | Xerox Corporation | PROCESS FOR PREPARING A LATEX EMULSION, DEVICE FOR THE PRODUCTION THEREOF AND TONER PRODUCTION METHOD |
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US9358513B2 (en) | 2013-04-10 | 2016-06-07 | Xerox Corporation | Method and system for magnetic actuated mixing |
US9656225B2 (en) | 2013-04-10 | 2017-05-23 | Xerox Corporation | Method and system for magnetic actuated mixing |
US20150086922A1 (en) * | 2013-09-24 | 2015-03-26 | Xerox Corporation | Latex forming process comprising concurrent steam injection emulsification and solvent distillation |
US9261801B2 (en) * | 2014-04-04 | 2016-02-16 | Xerox Corporation | Steam injection process for preparing polyester latex and apparatus thereof |
US10066115B2 (en) | 2014-07-10 | 2018-09-04 | Xerox Corporation | Magnetic actuated-milled pigment dispersions and process for making thereof |
US10087326B2 (en) | 2016-02-29 | 2018-10-02 | Michelman, Inc. | Aqueous-based hydrolytically stable dispersion of a biodegradable polymer |
Also Published As
Publication number | Publication date |
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RU2011124159A (en) | 2012-12-20 |
JP2012001718A (en) | 2012-01-05 |
CA2743155A1 (en) | 2011-12-21 |
US20110313079A1 (en) | 2011-12-22 |
JP5687139B2 (en) | 2015-03-18 |
CA2743155C (en) | 2013-12-31 |
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